Aminomethyl derivatives of p-hydroxybenzoic acid salts and amides



Patented May 26, 1942 f AMINOMETHVYL DERIVATIVES F P-HY- DROXYBENZOIC ACID SALTS AND AMIDES Louis H. Bock, Huntingdon Valley, Pa., assignor to Rohm-& Haas Company, Philadelphia, Pa.

No Drawing. Application April 22, 1941, 7 Serial No. 389,750

Claims. (01. 260-501) This invention relates to new condensation products of p-hydroxy-benzoic acid salts and amides with formaldehyde .and strongly basic secondary amines. This application a continuation-impart of my application Serial No. 272,133, filed May 6, 1939 which, on December 2, 1941, issued as U. S. Patent 2,264,358.

In the reaction of a phenol with formaldehyde and a strongly basic secondary amine it had been reported that, when thephenol possessed acidic substituents such as sulfonic,. aldehydro, or carboxyl groups, the desired condensation did not occur. In general, this appeared to be true but it isnow found, contrary to this generalization, that various series of interesting now products are obtainable from para-hydroxy-benzoic acid, its salts and amides including the N- substituted amides. This is all the more unexpected in view of the fact that salicylic acid and its esters and amides do not thusfcondense.

The condensation of p-hydroiry-benz'oic; acid,

its salts and its amides; formaldehyde and a strongly basic, non-aromaticfsecondary amine may be conducted in the presence or in the absence of solvents. Suitable proportions of reactants are mixed and warmed while the mixture is stirred. In place of formaldehyde there may be used one of the simple polymers of formaldehyde, such as para-formaldehyde. Such materials are, as is well known, equivalent to formaldehyde. It thus becomes possible to use anhydrous reagents, if desired. and to remove water of condensation during the course of the reaction.

The amines which react to give condensation products with formaldehyde and p-hydroxybenzcic acid, its salts and its amides include secondary amines of the aliphatic. alicyclic, and heterocyclic series, such as dimethylamine, di-

' ethylamine. dibutylamine, diamylamine, diallylamine, methyl dodecylamine, dicyclohexylamine, morpholine, piperidine, piperazine, pyrrclidine, diethanolamine, triethylene tetramine, and the like.

The para-hydroxy-benzoic acid amide used in the condensation may be the simple acid amide or one of the substituted amides containing one or more N-substituents, such as aliphatic, alicyclic, aryl, or aryl alkyl groups. As a salt there may be used a metal salt, an ammonium salt,'or an amine salt.

When one mol of p-hydroxy-benzoic acid, its

salt or its'amide is reacted withabout one mol of formaldehyde and about one mol of a secondary amine, the resulting compound has the general formula OH A V wherein R represents an acid amide or monoor di-substituted 'amide group, CONR R-c, (R1 and R2 being hydrogen or hydrocarbon) or a carboxylic acid salt group}, COM or -COI-I.amine (M representing a metallic ion).

and A and, B represent members of the group consisting of aliphatic hydrocarbon groups-and divalent groups which jointly with the nitrogen form a heterocyclic ring.

Typical examples of compounds of this type are represented by the following:

.7 a v V, I w

HO 0 V.

" ONe "on.

ONE

H: i/CH:

CHa

0H.HN(om H:

0K CH:

27 parts or p-hydroxybenzoic acid was dis.-

Example 2 A mixture consisting of parts of the cyclohexylamide of p-hydroxy-benzoic acid, 10 parts of a 30% aqueous solution of formaldehyde,

partsof a aqueous solution of dimethylamine'and parts of methanol was stirred at emulsifying, and penetrating agents.

CHa I CH:

./CHa' N\ I f .cm

Q 0 02H; 7 10 H0 7 CN\ (g CzH-t Ha CH: N/ a v, -1

1 a 1 a 7 CH: V ,i e .7 It is possible to introduce two methylene amine groups into the p-hydroxy-benzoic acid nucleus to obtain such a product as CH2N (CH:)2 H. i

0 H .CHQGHI II l H0 o-1-r .CH\ on,

A} 7 CHzCHa on; N\

In this case at least two mol equivalents or forma ldeh ydecand of secondary amine are reacted thnne m lie al nte t b-hydiqii-benzdic acidqits-salt or-ainida- I I friur-ther details of the preparation .of typical condensates Willi-be foundin the following illustrative- -examples, tin which the parts given are Example 1' T solved in parts 'of a 25% aqueous solution of dimethylamine; To this solution was added 16; parts of a 37% aqueous solution of formaldehyde. The mixture wasstirred several hours at room temperature; Theizproduct is soluble in water and is not precipitated by acidifying with 59 C. for.s ig:l 1 ou rs. The solution was vacuumconcentrated to liquid, which was insoluble in water but soluble in dilute acetic acid.

These new compounds may be used as wetting, Amides derived, from amines of high molecular weight arefuseful as detergents and emulsifying agents. Otherpossible uses include textile finishing agents; dye assistants, 'bactericides, -m0thioides, etc. As-shown inco pending applications Serial Nos. 248,196and v254,884,- compounds of thistype are useful for insolubilizing starch andother sizing materials and; ,in-thecase of .the higher 'moleculahmembers, for water-proofing; .textile fabricsJQ 7 1. A compound selected fromethe .group vcon.- sisting of gi-hydroxybenzoicuacidsalts. and mides in wh h a vlea onaq e .h dr a toms ortho to the phenolic hydro ryl group is replaced by anon-aromatic tertiary aminomethyl group.

2. A compound selected :from'the group con- 's isti'ngof 4-hydroxyben2oic acid salts and amides infwhich'fat least one of'th'ehydro'gen atoms ortho to they phenolic hydrox'yl group is replaced by adimethylaminomethyl'groupl' 74;;Thesodium salt ofB-dimethiylaminomethyl- 

